JP6158039B2 - Rubber composition and tire using the same - Google Patents
Rubber composition and tire using the same Download PDFInfo
- Publication number
- JP6158039B2 JP6158039B2 JP2013224176A JP2013224176A JP6158039B2 JP 6158039 B2 JP6158039 B2 JP 6158039B2 JP 2013224176 A JP2013224176 A JP 2013224176A JP 2013224176 A JP2013224176 A JP 2013224176A JP 6158039 B2 JP6158039 B2 JP 6158039B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- group
- rubber composition
- carbon atoms
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001971 elastomer Polymers 0.000 title claims description 103
- 239000005060 rubber Substances 0.000 title claims description 103
- 239000000203 mixture Substances 0.000 title claims description 54
- 239000011256 inorganic filler Substances 0.000 claims description 33
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 10
- 229920003051 synthetic elastomer Polymers 0.000 claims description 10
- 239000005061 synthetic rubber Substances 0.000 claims description 10
- 244000043261 Hevea brasiliensis Species 0.000 claims description 9
- 229920003052 natural elastomer Polymers 0.000 claims description 9
- 229920001194 natural rubber Polymers 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 33
- 239000000377 silicon dioxide Substances 0.000 description 16
- -1 amine compound Chemical class 0.000 description 15
- 238000013329 compounding Methods 0.000 description 8
- 239000004636 vulcanized rubber Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000020169 heat generation Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- VVPIUZNJHJQOGE-UHFFFAOYSA-N 2-[methyl-[3-(octadecanoylamino)propyl]amino]ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCN(C)CCOC(=O)CCCCCCCCCCCCCCCCC VVPIUZNJHJQOGE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZMKNQXCIMCSUDG-UHFFFAOYSA-N 2-[3-(dodecanoylamino)propyl-methylamino]ethyl dodecanoate Chemical compound C(CCCCCCCCCCC)(=O)NCCCN(C)CCOC(CCCCCCCCCCC)=O ZMKNQXCIMCSUDG-UHFFFAOYSA-N 0.000 description 1
- UOQYWMZLTNEIFI-UHFFFAOYSA-N 2-[3-aminopropyl(methyl)amino]ethanol Chemical compound OCCN(C)CCCN UOQYWMZLTNEIFI-UHFFFAOYSA-N 0.000 description 1
- IKBFHCBHLOZDKH-UHFFFAOYSA-N 2-chloroethyl(triethoxy)silane Chemical compound CCO[Si](CCCl)(OCC)OCC IKBFHCBHLOZDKH-UHFFFAOYSA-N 0.000 description 1
- CASYTJWXPQRCFF-UHFFFAOYSA-N 2-chloroethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCl CASYTJWXPQRCFF-UHFFFAOYSA-N 0.000 description 1
- 125000006031 2-methyl-3-butenyl group Chemical group 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DVNPFNZTPMWRAX-UHFFFAOYSA-N 2-triethoxysilylethanethiol Chemical compound CCO[Si](CCS)(OCC)OCC DVNPFNZTPMWRAX-UHFFFAOYSA-N 0.000 description 1
- LOSLJXKHQKRRFN-UHFFFAOYSA-N 2-trimethoxysilylethanethiol Chemical compound CO[Si](OC)(OC)CCS LOSLJXKHQKRRFN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XYKNGYCQUIQASK-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)propyl-(dimethoxymethyl)silane Chemical compound C1=CC=C2SC(CCC[SiH2]C(OC)OC)=NC2=C1 XYKNGYCQUIQASK-UHFFFAOYSA-N 0.000 description 1
- KQVVPOMBWBKNRS-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)propyl-triethoxysilane Chemical compound C1=CC=C2SC(CCC[Si](OCC)(OCC)OCC)=NC2=C1 KQVVPOMBWBKNRS-UHFFFAOYSA-N 0.000 description 1
- IABJHLPWGMWHLX-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)propyl-trimethoxysilane Chemical compound C1=CC=C2SC(CCC[Si](OC)(OC)OC)=NC2=C1 IABJHLPWGMWHLX-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- ZLAOXGYWRBSWOY-UHFFFAOYSA-N 3-chloropropyl(methoxy)silane Chemical compound CO[SiH2]CCCCl ZLAOXGYWRBSWOY-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- 125000006032 3-methyl-3-butenyl group Chemical group 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- AKQWHIMDQYDQSR-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylthiirane-2-carboxylate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C1(C)CS1 AKQWHIMDQYDQSR-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OMIBMQBWPBHDSI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)(=O)NCCCN(CC)CCOC(CCCCCCCCCCCCCCCCC)=O Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)NCCCN(CC)CCOC(CCCCCCCCCCCCCCCCC)=O OMIBMQBWPBHDSI-UHFFFAOYSA-N 0.000 description 1
- FSPIGXNLDXWYKZ-UHFFFAOYSA-N CCO[Si](CCC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CCC[Si](OCC)(OCC)OCC)(OCC)OCC Chemical compound CCO[Si](CCC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CCC[Si](OCC)(OCC)OCC)(OCC)OCC FSPIGXNLDXWYKZ-UHFFFAOYSA-N 0.000 description 1
- SXLPVOKGQWNWFD-UHFFFAOYSA-N CCO[Si](CC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CC[Si](OCC)(OCC)OCC)(OCC)OCC Chemical compound CCO[Si](CC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CC[Si](OCC)(OCC)OCC)(OCC)OCC SXLPVOKGQWNWFD-UHFFFAOYSA-N 0.000 description 1
- ZZOXWBGGPBLVNQ-UHFFFAOYSA-N CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC Chemical compound CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC ZZOXWBGGPBLVNQ-UHFFFAOYSA-N 0.000 description 1
- SKFGZHGVWONCTD-UHFFFAOYSA-N CN(C)C(SSSSC(N(C)C)=[S+]CCC[Si](OC)(OC)OC)=[S+]CCC[Si](OC)(OC)OC Chemical compound CN(C)C(SSSSC(N(C)C)=[S+]CCC[Si](OC)(OC)OC)=[S+]CCC[Si](OC)(OC)OC SKFGZHGVWONCTD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GSYVJAOBRKCNOT-UHFFFAOYSA-N diethoxymethyl-[3-[3-(diethoxymethylsilyl)propyltetrasulfanyl]propyl]silane Chemical compound CCOC(OCC)[SiH2]CCCSSSSCCC[SiH2]C(OCC)OCC GSYVJAOBRKCNOT-UHFFFAOYSA-N 0.000 description 1
- FSAKRVJHJMUPNR-UHFFFAOYSA-N dimethoxymethyl(3-nitropropyl)silane Chemical compound COC(OC)[SiH2]CCC[N+]([O-])=O FSAKRVJHJMUPNR-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- FPBXRRDHCADTAL-UHFFFAOYSA-N triethoxy(3-nitropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC[N+]([O-])=O FPBXRRDHCADTAL-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- QPPXVBLDIDEHBA-UHFFFAOYSA-N trimethoxy(3-nitropropyl)silane Chemical compound CO[Si](OC)(OC)CCC[N+]([O-])=O QPPXVBLDIDEHBA-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゴム組成物及びそれを用いたタイヤに関し、更に詳しくは、ゴム組成物へのシリカ等の無機充填剤の分散性を改良し、未加硫ゴムの粘度低減を実現しつつ、加硫ゴムの発熱性悪化を防止するゴム組成物及びそれを用いたタイヤに関する。 The present invention relates to a rubber composition and a tire using the rubber composition. More specifically, the present invention improves the dispersibility of an inorganic filler such as silica in the rubber composition and achieves a reduction in viscosity of unvulcanized rubber while increasing the viscosity. The present invention relates to a rubber composition that prevents exothermic deterioration of vulcanized rubber and a tire using the same.
近年の省エネルギーの社会的な要請に伴い、自動車の燃料消費節約を目的として、タイヤ用ゴム組成物の低発熱性と湿潤路面でのグリップ性を両立させる充填剤として、シリカ等の無機充填剤の配合が多用されている。 With the recent social demand for energy saving, for the purpose of saving fuel consumption of automobiles, inorganic fillers such as silica are used as fillers that achieve both low heat generation of tire rubber compositions and gripping properties on wet road surfaces. Formulation is frequently used.
無機充填剤は、その表面が親水的であるため、ゴム組成物中で粒子同士が凝集する傾向にあり、ゴム中への無機充填剤の分散を良くするためには混練時間を長くする必要がある。また、ゴム中への無機充填剤の分散が不十分なためゴム組成物のムーニー粘度が高くなり、押出しなどの加工性に劣るなどの欠点を有していた。さらに、シリカ等の粒子表面が酸性の無機充填剤を用いた場合は、一般的に塩基性を有することが多い加硫促進剤をその表面に吸着し、ゴム組成物の加硫が十分に行われず、貯蔵弾性率が上がらないことが多いという欠点を有していた。以上の背景により、従来から無機充填剤配合ゴム組成物における加工性等の改良が求められている。 Since the surface of the inorganic filler is hydrophilic, the particles tend to aggregate in the rubber composition, and it is necessary to lengthen the kneading time in order to improve the dispersion of the inorganic filler in the rubber. is there. Further, since the inorganic filler is not sufficiently dispersed in the rubber, the Mooney viscosity of the rubber composition is increased and the processability such as extrusion is inferior. Further, when an inorganic filler having an acidic particle surface such as silica is used, a vulcanization accelerator, which is generally basic, is adsorbed on the surface to sufficiently vulcanize the rubber composition. In other words, the storage elastic modulus often does not increase. In view of the above background, there has been a demand for improvement in processability and the like in an inorganic filler-containing rubber composition.
従来において、無機充填剤配合ゴム組成物における諸物性等を改良する技術として、例えば、シリカのゴム中への分散性の改良と、発熱性及び耐摩耗性が改良されたゴム組成物及びそれを用いた空気入りタイヤを提供するために、（Ａ）天然ゴム及び／又はジエン系合成ゴムからなるゴム成分１００重量部に対し、シリカ１５〜８５重量部と、ジメチルアルキルアミン等の特定の３級アミン化合物を前記シリカの量に対して１〜１５重量％配合してなる組成物、並びにそれをタイヤトレッドに用いた空気入りタイヤ（例えば、本願出願人の特許文献１参照）が知られている。 Conventionally, as a technique for improving various physical properties and the like in an inorganic filler-containing rubber composition, for example, improvement of dispersibility of silica in rubber, rubber composition with improved heat generation and wear resistance, and In order to provide the used pneumatic tire, (A) 15 to 85 parts by weight of silica with respect to 100 parts by weight of a rubber component made of natural rubber and / or diene synthetic rubber, and a specific tertiary such as dimethylalkylamine A composition obtained by blending 1 to 15% by weight of an amine compound with respect to the amount of silica, and a pneumatic tire using the composition for a tire tread (for example, see Patent Document 1 of the present applicant) are known. .
しかしながら、上記特許文献１のゴム組成物は、従来にないシリカのゴム中への分散性の改良と、発熱性及び耐摩耗性の改良がもたらされるものであるが、無機充填剤が配合されたゴム組成物において、更なる加硫ゴムの低発熱性を犠牲としない未加硫ゴムの粘度低減の実現が切望されている。 However, the rubber composition of the above-mentioned Patent Document 1 is improved in dispersibility of silica in rubber and improved in heat generation and wear resistance, but contains an inorganic filler. In rubber compositions, there is an urgent need to reduce the viscosity of unvulcanized rubber without sacrificing the low exothermic properties of further vulcanized rubber.
本発明は、上記従来技術の課題等について、これを解消しようとするものであり、ゴム組成物へのシリカの分散性を更に改良し、未加硫ゴムの粘度低減と、加硫ゴムの低発熱性を維持することができるゴム組成物及びそれを用いたタイヤ、並びに、未加硫ゴムの粘度低減方法を提供することを目的とする。 The present invention intends to solve the above-mentioned problems of the prior art, further improve the dispersibility of silica in the rubber composition, reduce the viscosity of unvulcanized rubber, and reduce the viscosity of vulcanized rubber. It is an object of the present invention to provide a rubber composition capable of maintaining exothermic properties, a tire using the same, and a method for reducing the viscosity of unvulcanized rubber.
本発明者らは、上記従来技術の課題等に鑑み、鋭意検討した結果、無機充填剤を含有するゴム成分に対して、特定の化合物の少なくとも一種を配合することにより、上記目的のゴム組成物及びこれを用いたタイヤ、並びに、未加硫ゴムの粘度低減方法が得られることを見出し、本発明を完成するに至ったのである。 As a result of intensive investigations in view of the above-described problems of the prior art, the present inventors have formulated a rubber composition for the above purpose by blending at least one specific compound with a rubber component containing an inorganic filler. And it discovered that the viscosity reduction method of a tire using this and this and an unvulcanized rubber was obtained, and came to complete this invention.
すなわち、本発明は、次の（１）〜（５）に存する。
（１） 天然ゴム及び／又はジエン系合成ゴムから選択される少なくとも一種のゴム成分に対して、無機充填剤と、下記式（Ｉ）で表される化合物の少なくとも一種を配合してなることを特徴とするゴム組成物。
（２） 前記ゴム成分１００質量部に対し、無機充填剤を５〜２００質量部、上記式（Ｉ）で表される化合物の少なくとも一種を０．５〜１５質量部配合してなることを特徴とする上記（１）記載のゴム組成物。
（３） 更に、シランカップリング剤を配合することを特徴とする上記（１）又は（２）に記載のゴム組成物。
（４） 上記（１）〜（３）の何れか一つに記載のゴム組成物をタイヤ部材に用いてなることを特徴とするタイヤ。
（５） 天然ゴム及び／又はジエン系合成ゴムから選択される少なくとも一種のゴム成分に対して、無機充填剤と、下記式（Ｉ）で表される化合物の少なくとも一種を配合する、未加硫ゴムの粘度低減方法。
(1) An inorganic filler and at least one compound represented by the following formula (I) are blended with at least one rubber component selected from natural rubber and / or diene synthetic rubber. A rubber composition.
(2) The inorganic component is blended in an amount of 5 to 200 parts by mass and at least one compound represented by the above formula (I) is blended in an amount of 0.5 to 15 parts by mass with respect to 100 parts by mass of the rubber component. The rubber composition according to (1) above.
(3) The rubber composition as described in (1) or (2) above, further comprising a silane coupling agent.
(4) A tire comprising the rubber composition according to any one of (1) to (3) above as a tire member.
(5) An unvulcanized compound in which at least one rubber component selected from natural rubber and / or diene-based synthetic rubber is blended with an inorganic filler and at least one compound represented by the following formula (I) A method for reducing the viscosity of rubber.
本発明によれば、ゴム組成物への無機充填剤の分散性を改良し、未加硫ゴムの粘度低減と、加硫ゴムの低発熱性を維持できるゴム組成物及びそれを用いたタイヤ、並びに、未加硫ゴムの粘度低減方法が提供される。 According to the present invention, the rubber composition capable of improving the dispersibility of the inorganic filler in the rubber composition, reducing the viscosity of the unvulcanized rubber, and maintaining the low heat buildup of the vulcanized rubber, and the tire using the rubber composition, A method for reducing the viscosity of unvulcanized rubber is also provided.
以下に、本発明の実施形態を詳しく説明する。
本発明のゴム組成物は、天然ゴム及び／又はジエン系合成ゴムから選択される少なくとも一種のゴム成分に対して、無機充填剤と、下記式（Ｉ）で表される化合物の少なくとも一種を配合してなることを特徴とするものである。
The rubber composition of the present invention contains an inorganic filler and at least one compound represented by the following formula (I) with respect to at least one rubber component selected from natural rubber and / or diene synthetic rubber. It is characterized by being formed.
本発明のゴム組成物に用いるゴム成分は、天然ゴム及び／又はジエン系合成ゴムからなる。ここで、ジエン系合成ゴムとしては、ポリイソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）、スチレン-ブタジエン共重合体ゴム（ＳＢＲ）、ブチルゴム（ＩＩＲ）、エチレン-プロピレン共重合体等が挙げられる。これらのゴム成分は、一種単独で用いても、二種以上をブレンドして用いてもよい。 The rubber component used in the rubber composition of the present invention comprises natural rubber and / or diene synthetic rubber. Here, examples of the diene-based synthetic rubber include polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), butyl rubber (IIR), and ethylene-propylene copolymer. These rubber components may be used alone or in a blend of two or more.
本発明のゴム組成物に用いる無機充填剤としては、シリカ、水酸化アルミニウム、アルミナ、クレー、炭酸カルシウム等が挙げられ、これらの中でも、補強性の観点から、シリカ及び水酸化アルミニウムが好ましく、シリカが特に好ましい。
用いることができるシリカとしては、特に制限はなく、市販のゴム組成物に使用されているものが使用でき、中でも湿式シリカ（含水ケイ酸）、乾式シリカ（無水ケイ酸）、コロイダルシリカ等を使用することができ、特に、湿式シリカの使用が好ましい。
Examples of the inorganic filler used in the rubber composition of the present invention include silica, aluminum hydroxide, alumina, clay, calcium carbonate and the like. Among these, silica and aluminum hydroxide are preferable from the viewpoint of reinforcing properties. Is particularly preferred.
Silica that can be used is not particularly limited, and those used in commercially available rubber compositions can be used, among which wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), colloidal silica, etc. are used. In particular, the use of wet silica is preferred.
これらの無機充填剤の配合量は、上記ゴム成分１００質量部に対して５〜２００質量部の範囲が好ましく、更に好ましくは、５〜１５０質量部の範囲とすることが望ましく、より更に好ましくは、５０〜１２０質量部の範囲とすることが望ましい。
この無機充填剤の配合量が上記ゴム成分１００質量部に対してウェットグリップ向上とヒステリシスを低下を両立させる効果の観点から、５質量部以上が好ましく、一方、粘度を低下させる観点から２００質量部以下が好ましい。
The blending amount of these inorganic fillers is preferably in the range of 5 to 200 parts by weight, more preferably in the range of 5 to 150 parts by weight, even more preferably, with respect to 100 parts by weight of the rubber component. 50 to 120 parts by mass is desirable.
The amount of the inorganic filler is preferably 5 parts by mass or more from the viewpoint of achieving both an improvement in wet grip and a decrease in hysteresis with respect to 100 parts by mass of the rubber component, while 200 parts by mass from the viewpoint of reducing the viscosity. The following is preferred.
本発明のゴム組成物には、補強性の観点から、シランカップリング剤を配合することが好ましい。
用いることができるシランカップリング剤は、特に制限なく、例えば、ビス（３−トリエトキシシリルプロピル）テトラスルフィド、ビス（３−トリエトキシシリルプロピル）トリスルフィド、ビス（３−トリエトキシシリルプロピル）ジスルフィド、ビス（２−トリエトキシシリルエチル）テトラスルフィド、ビス（３−トリメトキシシリルプロピル）テトラスルフィド、ビス（２−トリメトキシシリルエチル）テトラスルフィド、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、２−メルカプトエチルトリメトキシシラン、２−メルカプトエチルトリエトキシシラン、３−ニトロプロピルトリメトキシラン、３−ニトロプロピルトリエトキシシラン、３−クロロプロピルメトキシシラン、３−クロロプロピルトリエトキシシラン、２−クロロエチルトリメトキシシラン、２−クロロエチルトリエトキシシラン、３−トリメトキシシリルプロピル−Ｎ，Ｎ−ジメチルチオカルバモイルテトラスルフィド、３−トリエトキシシリルプロピル−Ｎ，Ｎ−ジメチルチオカルバモイルテトラスルフィド、２−トリエトキシシリルエチル−Ｎ，Ｎ−ジメチルチオカルバモイルテトラスルフィド、３−トリメトキシシリルプロピルベンゾチアゾールテトラスルフィド、３−トリエトキシシリルプロピルベンゾチアゾールテトラスルフィド、３−トリエトキシシリルプロピルメタクリレートモノスルフィド、３−トリメトキシシリルプロピルメタクリレートモノスルフィド、ビス（３−ジエトキシメチルシリルプロピル）テトラスルフィド、３−メルカプトプロピルジメトキシメチルシラン、３−ニトロプロピルジメトキシメチルシラン、３−クロロプロピルジメトキシメチルシラン、ジメトキシメチルシリルプロピル−Ｎ，Ｎ−ジメチルチオカルバモイルテトラスルフィド、ジメトキシメチルシリルプロピルベンゾチアゾールテトラスルフィドなどの少なくとも１種が挙げられる。
It is preferable to mix | blend a silane coupling agent with the rubber composition of this invention from a reinforcement viewpoint.
The silane coupling agent that can be used is not particularly limited, and examples thereof include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, and bis (3-triethoxysilylpropyl) disulfide. Bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Ethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane, 3-chloropropylmethoxysilane, 3- Lolopropyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N- Dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilyl Propyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mer At least one of ptopropyldimethoxymethylsilane, 3-nitropropyldimethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazole tetrasulfide, etc. Is mentioned.
これらのシランカップリング剤の配合量は、無機充填剤１００質量部に対し、補強性の観点から、１質量部以上が好ましく、一方、補強性、発熱性を維持する観点から、２０質量部以下が好ましく、更に好ましくは、発熱性の観点から、６〜１２質量部の範囲が望ましい。 The blending amount of these silane coupling agents is preferably 1 part by mass or more from the viewpoint of reinforcing properties with respect to 100 parts by mass of the inorganic filler, while 20 parts by mass or less from the viewpoint of maintaining reinforcing properties and heat generation. More preferably, the range of 6 to 12 parts by mass is desirable from the viewpoint of heat generation.
本発明では、上記無機充填剤と共に補強性充填剤として、カーボンブラックなどを併用できる。
用いることができるカーボンブラックは、特に制限なく、例えば、ＦＥＦ、ＳＲＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦなどのグレードを用いることができる。
これらのカーボンブラックの配合量も、特に限定されるものではないが、好ましくは、前記ゴム成分１００質量部に対し、０〜６０質量部、更に好ましくは、１０〜５０質量部であることが望ましい。なお、発熱性を維持する観点から、６０質量部以下が好ましい。
In this invention, carbon black etc. can be used together as a reinforcing filler with the said inorganic filler.
Carbon black that can be used is not particularly limited, and grades such as FEF, SRF, HAF, ISAF, and SAF can be used.
The blending amount of these carbon blacks is also not particularly limited, but is preferably 0 to 60 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the rubber component. . In addition, 60 mass parts or less are preferable from a viewpoint of maintaining exothermic property.
本発明に用いる下記式（Ｉ）で表される化合物は、無機充填剤配合ゴムの未加硫ゴム粘度低減と、加硫ゴムの発熱性を改良して本発明の効果を発揮させるために配合するものである。
上記式（Ｉ）において、Ｒ１、Ｒ２、Ｒ４は、炭素数１〜２４のアルキル基又はアルケニル基を表し、該炭素数１〜２４のアルキル基及びアルケニル基は、直鎖状、分枝鎖状及び環状の何れでもよく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、２−エチルヘキシル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、イソウンデシル基、ドデシル基、イソドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、イソテトラデシル基、ヘキサデシル基、イソヘキサデシル基、ヘプタデシル基、イソヘプタデシル基、オクタデシル基、イソオクタデシル基、ノナデシル基、アイコシル基、ドコシル基、テトラコシル基などのアルキル基、アリル基、３−ブテニル基、メタリル基、２−メチル−３−ブテニル基、３−メチル−３−ブテニル基、１，１，−ジメチル−２−プロペニル基、４−ペンテニル基、オレイル基、テトラコシリレン基などのアルケニル基が挙げられ、好ましくは、炭素数６〜１８、さらに好ましくは炭素数１１〜１８、より更に好ましくは炭素数１４〜１８のアルキル基又はアルケニル基であり、該アルキル基及びアルケニル基は直鎖状、分枝鎖状及び環状の何れでもよく、ヘプチル基、２−エチルヘキシル基、ウンデシル基、トリデシル基、ペンタデシル基、ヘプタデシル基、ヘプタデセニル基である。Ｒ２及びＲ４の由来となる脂肪酸としては、好ましくは、オクタン酸、ラウリン酸、テトラデカン酸、ミリスチン酸、ステアリン酸、オレイン酸等が挙げられる。 In the above formula (I), R 1 , R 2 and R 4 represent an alkyl group or alkenyl group having 1 to 24 carbon atoms, and the alkyl group and alkenyl group having 1 to 24 carbon atoms are linear, Any of branched and cyclic groups may be used, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, Isoheptyl, octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, dodecyl, isododecyl, tridecyl, isotridecyl, tetradecyl, isotetradecyl, hexadecyl Group, isohexadecyl group, heptadecyl group, isoheptadecyl group, octadecyl group, Tadecyl group, nonadecyl group, eicosyl group, docosyl group, tetracosyl group and other alkyl groups, allyl group, 3-butenyl group, methallyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, 1, Examples include alkenyl groups such as 1, -dimethyl-2-propenyl group, 4-pentenyl group, oleyl group and tetracosilylene group, preferably 6 to 18 carbon atoms, more preferably 11 to 18 carbon atoms, and still more. Preferably, it is an alkyl group or alkenyl group having 14 to 18 carbon atoms, and the alkyl group and alkenyl group may be any of linear, branched and cyclic, and heptyl group, 2-ethylhexyl group, undecyl group, tridecyl group. Group, pentadecyl group, heptadecyl group and heptadecenyl group. Preferred examples of fatty acids from which R 2 and R 4 are derived include octanoic acid, lauric acid, tetradecanoic acid, myristic acid, stearic acid, and oleic acid.
更に、上記式（Ｉ）中のＲ３及びＲ５は、炭素数２〜５のアルキレン基を表すものである。上記炭素数２〜５のアルキレン基は、直鎖状、分枝鎖状及び環状の何れでもよく、例えば、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ｔ−ブチレン基、ペンチレン基などのアルキレン基が挙げられ、好ましくは、炭素数２〜３のアルキレン基であり、該アルキレン基は直鎖状、分枝鎖状及び環状の何れでもよい。また、ｎは１〜５の数であり、好ましくは、ｎは１〜３の数である。 Furthermore, R 3 and R 5 in the above formula (I) represent an alkylene group having 2 to 5 carbon atoms. The alkylene group having 2 to 5 carbon atoms may be any of linear, branched and cyclic, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, t-butylene. And alkylene groups such as a pentylene group, preferably an alkylene group having 2 to 3 carbon atoms, which may be linear, branched or cyclic. N is a number from 1 to 5, and preferably n is a number from 1 to 3.
本発明において、上記式（Ｉ）で表される化合物として、特に好ましいものとしては、上記Ｒ１が炭素数１〜８のアルキル基又はアルケニル基であり、Ｒ２およびＲ４が炭素数８〜２２のアルキル基又はアルケニル基であり、Ｒ３およびＲ５が炭素数２〜４のアルキレン基であり、となる化合物の少なくとも１種が望ましい。
具体的に用いることができる上記式（Ｉ）で表される化合物としては、例えば、Ｎ−ラウロイルアミノプロピル−Ｎ−ラウロイルオキシエチル−Ｎ−メチルアミン、Ｎ−ラウロイルアミノプロピル−Ｎ−ラウロイルオキシエチル−Ｎ−エチルアミン、Ｎ−ステアロイルアミノプロピル−Ｎ−ステアロイルオキシエチル−Ｎ−メチルアミン、Ｎ−ステアロイルアミノプロピル−Ｎ−ステアロイルオキシエチル−Ｎ−エチルアミンの少なくとも１種を挙げることができ、中でも、Ｎ−ステアロイルアミノプロピル−Ｎ−ステアロイルオキシエチル−Ｎ−メチルアミンの使用が望ましい。
上記式（Ｉ）で表される化合物の分子量としては、未加硫ゴム粘度低減の観点から、２０１〜５０００のものが好ましく、２００〜３０００のものがさらに好ましく、３００〜１５００のものが特に好ましい。
なお、上記式（Ｉ）で表される化合物の合成法は、既知であり、種々の製法により得ることができ、また、市販のものを使用してもよい。
In the present invention, as the compound represented by the above formula (I), particularly preferred are those in which R 1 is an alkyl group or alkenyl group having 1 to 8 carbon atoms, and R 2 and R 4 are 8 to 8 carbon atoms. 22 or an alkenyl group, R 3 and R 5 are each an alkylene group having 2 to 4 carbon atoms, and at least one of the following compounds is desirable.
Specific examples of the compound represented by the formula (I) that can be used include N-lauroylaminopropyl-N-lauroyloxyethyl-N-methylamine and N-lauroylaminopropyl-N-lauroyloxyethyl. At least one of -N-ethylamine, N-stearoylaminopropyl-N-stearoyloxyethyl-N-methylamine, N-stearoylaminopropyl-N-stearoyloxyethyl-N-ethylamine, The use of -stearoylaminopropyl-N-stearoyloxyethyl-N-methylamine is desirable.
The molecular weight of the compound represented by the formula (I) is preferably 201 to 5000, more preferably 200 to 3000, and particularly preferably 300 to 1500 from the viewpoint of reducing the viscosity of the unvulcanized rubber. .
In addition, the synthesis | combining method of the compound represented by the said formula (I) is known, can be obtained by various manufacturing methods, and may use a commercially available thing.
これらの化合物の少なくとも一種の配合量は、好ましくは、ゴム成分１００質量部に対して、０．５〜１５質量部、更に好ましくは、本発明の更なる効果を発揮せしめる観点から、１〜１５質量部が好ましく、３〜１０質量部がより好ましい。また、これらの化合物の少なくとも一種の配合量は、無機充填剤１００質量部に対して、０．５〜２０質量部が好ましく、１〜１５質量部がより好ましく、２〜１２質量部がより更に好ましく、３〜１０質量部がより好ましく、３〜８質量部がより更に好ましい。
この化合物の少なくとも一種の配合量が、ゴム成分１００質量部に対して、０．５質量部以上では、未加硫ゴム粘度低減効果が高く、一方、１５質量部を越えると、加硫速度への影響が大きくなる。
The compounding amount of at least one of these compounds is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the rubber component, more preferably 1 to 15 from the viewpoint of exerting further effects of the present invention. A mass part is preferable and 3-10 mass parts is more preferable. Moreover, 0.5-20 mass parts is preferable with respect to 100 mass parts of inorganic fillers, as for the compounding quantity of at least 1 type of these compounds, 1-15 mass parts is more preferable, and 2-12 mass parts is still more. Preferably, 3-10 mass parts is more preferable, and 3-8 mass parts is still more preferable.
When the compounding amount of at least one compound is 0.5 parts by mass or more with respect to 100 parts by mass of the rubber component, the effect of reducing the viscosity of the unvulcanized rubber is high. The effect of.
本発明のゴム組成物には、上記ゴム成分、無機充填剤、上記式（Ｉ）で表される化合物の他に、ゴム工業界で通常使用される配合剤、例えば、老化防止剤、軟化剤、ステアリン酸、亜鉛華、加硫促進剤、加硫促進助剤、加硫剤等を、本発明の目的を阻害しない範囲内で適宜選択して配合することができる。これら配合剤としては、市販品を好適に使用することができる。
また、本発明のゴム組成物は、ゴム成分と、無機充填剤と、上記化合物の少なくとも一種と、必要に応じて適宜選択した各種配合剤とをロール、インターナルミキサー等の混練り機を用いて混練り、熱入れ、押出等することにより得られ、成形加工後、加硫を行い、タイヤトレッド、アンダートレッド、カーカス、サイドウォール、ビード部分等の空気入りタイヤのタイヤ部材の用途を始め、防振ゴム、ベルト，ホースその他の工業製品等の用途にも用いることができる。
In the rubber composition of the present invention, in addition to the rubber component, the inorganic filler, and the compound represented by the formula (I), a compounding agent usually used in the rubber industry, such as an anti-aging agent and a softening agent. , Stearic acid, zinc white, vulcanization accelerator, vulcanization acceleration aid, vulcanizing agent, and the like can be appropriately selected and blended within a range not impairing the object of the present invention. As these compounding agents, commercially available products can be suitably used.
Further, the rubber composition of the present invention uses a kneader such as a roll, an internal mixer, etc., with a rubber component, an inorganic filler, at least one of the above compounds, and various compounding agents appropriately selected as necessary. Obtained by kneading, heating, extruding, etc., after molding, vulcanizing, starting with the use of tire members for pneumatic tires such as tire treads, under treads, carcass, sidewalls, bead parts, It can also be used for applications such as anti-vibration rubber, belts, hoses and other industrial products.
このように構成されるゴム組成物が、何故、ゴム組成物へのシリカの分散性を改良し、未加硫ゴムの粘度低減を実現しつつ、加硫ゴムの発熱性悪化を防止するものとなるかは以下のように推察される。
すなわち、本発明のゴム組成物において、天然ゴム及び／又はジエン系合成ゴムから選択される少なくとも一種のゴム成分に対して、無機充填剤を配合した配合系に、上記式（Ｉ）で表される化合物の少なくとも一種が配合されると、該化合物の分子構造に含まれるアミノ基、場合によってはさらにエステル基、アミド基、エーテル基等の効果により無機充填剤の表面に吸着し、無機充填剤表面を疎水化することにより、無機充填剤同士の凝集を抑制し、未加硫ゴムの粘度を低減し、また、無機充填剤表面での促進剤の吸着を抑制するため、発熱性も改良できて、加工性も良好となるものと推察される。
The rubber composition configured as described above improves the dispersibility of silica in the rubber composition and realizes a reduction in the viscosity of the unvulcanized rubber while preventing the exothermic deterioration of the vulcanized rubber. It is guessed as follows.
That is, the rubber composition of the present invention is represented by the above formula (I) in a compounding system in which an inorganic filler is blended with at least one rubber component selected from natural rubber and / or diene synthetic rubber. When at least one kind of compound is blended, it is adsorbed on the surface of the inorganic filler due to the effects of amino groups contained in the molecular structure of the compound, and in some cases, ester groups, amide groups, ether groups, and the like. By hydrophobizing the surface, the aggregation of inorganic fillers can be suppressed, the viscosity of unvulcanized rubber can be reduced, and the adsorption of accelerators on the surface of inorganic fillers can be suppressed. Therefore, it is presumed that processability is also improved.
次に、本発明のタイヤは、本発明のゴム組成物を用いて通常の方法によって製造される。すなわち、必要に応じて、上記のように各種配合剤を配合させた本発明のゴム組成物が未加硫の段階でタイヤ部材として、例えば、トレッド用部材に押出し加工され、タイヤ成形機上で通常の方法により貼り付け成形され、生タイヤが成形される。この生タイヤを加硫機中で加熱加圧して、タイヤが得られる。このようにして得られた本発明のタイヤは、低発熱性が維持できるので、低燃費性が良好であると共に、しかも該ゴム組成物の加工性が良好であるので、生産性にも優れたものとなる。
更に、本発明の未加硫ゴムの粘度低減方法は、天然ゴム及び／又はジエン系合成ゴムから選択される少なくとも一種のゴム成分に対して、無機充填剤と、上記式（Ｉ）で表される化合物の少なくとも一種を配合することを特徴とするものである。
本発明の未加硫ゴムの粘度低減方法で用いられる各成分の好ましい成分、好ましい範囲等は、前述のゴム組成物と同じである。
この未加硫ゴムの粘度低減方法によれば、無機充填剤表面の疎水化により、無機充填剤同士の凝集を抑制し、未加硫ゴムの粘度が低減されるものとなる。
Next, the tire of the present invention is produced by a usual method using the rubber composition of the present invention. That is, if necessary, the rubber composition of the present invention in which various compounding agents are blended as described above is extruded as a tire member at a non-vulcanized stage, for example, a tread member, and then on a tire molding machine. Paste molding is performed by a normal method, and a green tire is molded. The green tire is heated and pressed in a vulcanizer to obtain a tire. Since the tire of the present invention thus obtained can maintain low heat build-up, the fuel consumption is good and the processability of the rubber composition is good, so that the productivity is excellent. It will be a thing.
Furthermore, the method for reducing the viscosity of an unvulcanized rubber according to the present invention is represented by an inorganic filler and the above formula (I) with respect to at least one rubber component selected from natural rubber and / or diene synthetic rubber. It is characterized by blending at least one of the following compounds.
The preferred components, preferred ranges and the like of each component used in the method for reducing the viscosity of an unvulcanized rubber of the present invention are the same as those of the rubber composition described above.
According to this method for reducing the viscosity of an unvulcanized rubber, the surface of the inorganic filler is hydrophobized to suppress aggregation of the inorganic fillers, thereby reducing the viscosity of the unvulcanized rubber.
次に、実施例及び比較例を挙げて本発明を更に詳しく説明するが、本発明は下記実施例に何ら限定されるものではない。 EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to the following Example at all.
＜製造例＞
用いる化合物１は、下記製造法等により得たものを使用した。
（製造例１）
ステアリン酸；３４１．４ｇ（１．２モル）、Ｎ−メチル−Ｎ−ヒドロキシエチル−Ｎ−アミノプロピルアミン；７９．３ｇ（０．６モル）とを通常の方法により脱水縮合反応して、Ｎ−ステアロイルアミノプロピル−Ｎ−ステアロイルオキシエチル−Ｎ−メチルアミンを３６２ｇ得た。
<Production example>
The compound 1 used was obtained by the following production method or the like.
(Production Example 1)
Stearic acid; 341.4 g (1.2 mol), N-methyl-N-hydroxyethyl-N-aminopropylamine; 79.3 g (0.6 mol) were subjected to a dehydration condensation reaction by a conventional method, and N -362 g of stearoylaminopropyl-N-stearoyloxyethyl-N-methylamine was obtained.
〔実施例１〜３及び比較例１〕
下記表１に示す配合処方で常法により、ゴム組成物を調製した。表中の数値は質量部である。
得られた各ゴム組成物について、下記測定方法により、未加硫ゴム粘度の測定を行った。また、得られたゴム組成物を１６０℃で１４分間加硫した。得られた加硫ゴムに対し、下記測定方法により粘弾性（ｔａｎδ）の測定を行った。
これらの結果を下記表１に示す。
[Examples 1 to 3 and Comparative Example 1]
A rubber composition was prepared by a conventional method with the formulation shown in Table 1 below. The numerical value in a table | surface is a mass part.
About each obtained rubber composition, the unvulcanized rubber viscosity was measured with the following measuring method. Further, the obtained rubber composition was vulcanized at 160 ° C. for 14 minutes. The obtained vulcanized rubber was measured for viscoelasticity (tan δ) by the following measurement method.
These results are shown in Table 1 below.
〔未加硫ゴム粘度の測定方法〕
未加硫ゴム粘度は、ＪＩＳ Ｋ ６３００−１：２００１（ムーニー粘度）に準拠して行った。ローターサイズは一般的なＬサイズで行った。
なお、評価は、比較例１の値を１００として指数表示した。未加硫ゴム粘度は、値が小さいほど良好であることを示す。
[Measurement method of unvulcanized rubber viscosity]
The unvulcanized rubber viscosity was measured in accordance with JIS K 6300-1: 2001 (Mooney viscosity). The rotor size was a general L size.
The evaluation was expressed as an index with the value of Comparative Example 1 being 100. An unvulcanized rubber viscosity shows that it is so favorable that a value is small.
〔粘弾性（ｔａｎδ）の測定方法〕
粘弾性測定装置（レオメトリックス社製）を使用し、温度５０℃、歪み５％、周波数１５Ｈｚでｔａｎδを測定し、比較例１の値を１００として指数表示した。この値が小さい程、低発熱性が良好であることを示す。
[Measurement method of viscoelasticity (tan δ)]
Using a viscoelasticity measuring device (manufactured by Rheometrics), tan δ was measured at a temperature of 50 ° C., a strain of 5%, and a frequency of 15 Hz. It shows that low exothermic property is so favorable that this value is small.
上記表１の＊１〜＊１１は下記のとおりである。
＊１）タフデン２８３０〔旭化成ケミカルズ社製〕（ゴム成分１００質量部、油成分３７．５質量部）
＊２）シースト７ＨＭ〔東海カーボン社製〕
＊３）東ソーシリカ株式会社製「ニプシールＶＮ３」
＊４）ビス（３−トリエトキシシリルプロピル）テトラスルフィド
＊５）マイクロクリスタリンワックス、オゾエース０７０１〔日本精蝋社製〕
＊６）ノクラック６Ｃ〔大内新興化学工業社製〕
＊７）ノンフレックスＲＤ−Ｓ〔精工化学社製〕
＊８）ノクセラーＤ〔大内新興化学工業社製〕
＊９）ノクセラーＤＭ〔大内新興化学工業社製〕
＊１０）サンセラーＣＭ−Ｇ〔三新化学工業社製〕
＊１１）製造例１〔化学式（Ｉ）において、Ｒ１＝メチル基、Ｒ２，Ｒ４＝ステアリル基、Ｒ５＝エチレン基、Ｒ３＝プロピレン基、ｎ＝１の化合物、Ｎ−ステアロイルアミノプロピル−Ｎ−ステアロイルオキシエチル−Ｎ−メチルアミン〕
* 1 to * 11 in Table 1 are as follows.
* 1) Toughden 2830 (manufactured by Asahi Kasei Chemicals) (100 parts by mass of rubber component, 37.5 parts by mass of oil component)
* 2) Seast 7HM [Tokai Carbon Co., Ltd.]
* 3) “Nipseal VN3” manufactured by Tosoh Silica Corporation
* 4) Bis (3-triethoxysilylpropyl) tetrasulfide * 5) Microcrystalline wax, Ozoace 0701 (manufactured by Nippon Seiwa Co., Ltd.)
* 6) Nocrack 6C (Ouchi Shinsei Chemical Co., Ltd.)
* 7) Non-flex RD-S [Seiko Chemical Co., Ltd.]
* 8) Noxeller D [Ouchi Shinsei Chemical Co., Ltd.]
* 9) Noxeller DM (Ouchi Shinsei Chemical Co., Ltd.)
* 10) Sunseller CM-G [manufactured by Sanshin Chemical Industry Co., Ltd.]
* 11) Production Example 1 [In the chemical formula (I), R 1 = methyl group, R 2 , R 4 = stearyl group, R 5 = ethylene group, R 3 = propylene group, n = 1 compound, N-stearoylamino Propyl-N-stearoyloxyethyl-N-methylamine]
上記表１から明らかなように、本発明範囲となる実施例１〜３のゴム組成物は、本発明の範囲外となる比較例１に較べて、未加硫ゴム粘度、粘弾性（ｔａｎδ）の評価結果から、加硫ゴムの低発熱性を損なうことなく、未加硫ゴムの粘度低減効果が良好となるゴム組成物となることが判明した。 As is clear from Table 1 above, the rubber compositions of Examples 1 to 3 that fall within the scope of the present invention have a viscosity of unvulcanized rubber and viscoelasticity (tan δ) as compared with Comparative Example 1 that falls outside the scope of the present invention. From these evaluation results, it has been found that the rubber composition can have a good effect of reducing the viscosity of the unvulcanized rubber without impairing the low exothermic property of the vulcanized rubber.
タイヤトレッド、アンダートレッド、カーカス、サイドウォール、ビード部分等の空気入りタイヤのタイヤ部材の用途を始め、防振ゴム、ベルト、ホースなどのゴム製品に好適に用いることができる。 It can be suitably used for rubber products such as anti-vibration rubbers, belts, hoses, etc., as well as applications for tire members of pneumatic tires such as tire treads, under treads, carcass, sidewalls, and bead portions.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013224176A JP6158039B2 (en) | 2013-10-29 | 2013-10-29 | Rubber composition and tire using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013224176A JP6158039B2 (en) | 2013-10-29 | 2013-10-29 | Rubber composition and tire using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015086258A JP2015086258A (en) | 2015-05-07 |
| JP6158039B2 true JP6158039B2 (en) | 2017-07-05 |
Family
ID=53049427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013224176A Active JP6158039B2 (en) | 2013-10-29 | 2013-10-29 | Rubber composition and tire using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6158039B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6766484B2 (en) * | 2016-07-11 | 2020-10-14 | 横浜ゴム株式会社 | Rubber composition for tires and tires |
| JPWO2018105230A1 (en) * | 2016-12-08 | 2019-10-24 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5848942B2 (en) * | 2011-10-18 | 2016-01-27 | 株式会社ブリヂストン | Rubber composition and tire using the same |
-
2013
- 2013-10-29 JP JP2013224176A patent/JP6158039B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015086258A (en) | 2015-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5782456B2 (en) | Rubber composition and tire using the same | |
| JP5918780B2 (en) | Rubber composition and tire using the same | |
| WO2015166997A1 (en) | Rubber composition for tire, production method for rubber composition for tire, and tire | |
| JP6362546B2 (en) | Manufacturing method of tire rubber composition and tire | |
| JP2009013197A (en) | Rubber composition for inner liner and tire having inner liner using the same | |
| JP6878813B2 (en) | Rubber composition for base tread | |
| JP2013147581A (en) | Rubber composition and tire using the same | |
| JP5848942B2 (en) | Rubber composition and tire using the same | |
| JP6114067B2 (en) | Rubber composition and tire | |
| WO2012070625A1 (en) | Rubber composition and tire using the same | |
| JP6158039B2 (en) | Rubber composition and tire using the same | |
| JP6158038B2 (en) | Rubber composition and tire using the same | |
| JP7511392B2 (en) | Rubber composition, rubber composition for tires, crosslinked rubber for tires, additives for tires and rubber | |
| JP5869956B2 (en) | Rubber composition for tire | |
| JP2010059252A (en) | Studless tire for truck-bus or for light truck | |
| JP6358967B2 (en) | Manufacturing method of tire rubber composition and tire | |
| JP7197238B2 (en) | Additive for rubber, additive composition for rubber, rubber composition for tire, crosslinked rubber composition for tire, rubber product for tire, and tire | |
| JP5877758B2 (en) | Rubber composition for tire | |
| JP5848943B2 (en) | Rubber composition and tire using the same | |
| JP7511393B2 (en) | Rubber composition, rubber composition for tires, crosslinked rubber for tires, additives for tires and rubber | |
| JP2013224407A (en) | Rubber composition for tire, and tire | |
| JP2013173906A (en) | Rubber composition | |
| JP2008007679A (en) | Rubber composition for cap tread, and pneumatic tire having cap tread composed of the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160623 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170310 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170314 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170427 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170516 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170607 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6158039 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |